This invention relates to compositions containing an azole and an amine oxide and their use as wood preservative and waterproofing compositions and as fungicides in agricultural products.
Azoles are generally known to be effective as wood preservatives. Azole compounds are registered with the US Environmental Protection Agency (EPA) for use in wood protection treatment to buildings, forest products, finished wood products, log houses, wooden aquatic structures, wooden containers, and pressure treated forest products. Azoles are also used in industrial preservation applications and agriculture applications to protect plants, fruits, vegetables, cereal crops and sugar corps from fungal attack.
Azole compounds are lipophilic, due to their organic nature, and have good solubility in organic medium. However, they typically have poor solubility in aqueous solutions. According to xe2x80x9cThe Pesticide Manual, 11th Editionxe2x80x9d, C. D. S. Tomlin, editor, published by the British Crop Protection Council, UK (1997), the solubility of propiconazole in water is 100 ppm at 20xc2x0 C., and that of tebuconazole in water is 36 ppm at 20xc2x0 C. A number of wood preservation concentrates have recently been developed to circumvent the water solubility problem.
DE 19648888 describes water-thinned wood preservative concentrates containing at least 5% triazole fungicide in an aqueous benzalkonium halide solution, e.g., a 50% aqueous (C12-14 alkyl)benzyldimethyl ammonium chloride solution.
WO 98/18321 describes a microbicide microemulsion containing a solvating surfactant selected from alkoxylated castor oil, alkoxylated hydrogenated castor oil and an alkyoxylated rosin.
WO 98/00008 describes a liquid pesticidal composition containing azole compounds in an organic solvent and as surfactants (a) a castor oil ethoxylate having 30-50 mole ethoxylate, (b) a branched C8-C18 alcohol ethoxylate having 5-10 mole ethoxylate, and (c) a tristyrene phenol ethoxylate having 8-30 mole ethoxylate or its phosphate or salt.
DE 4441672 describes wood preservative compositions containing a dimethylalkylamine, an aliphatic C8-C20 dicarboxylic acid, propylene glycol and a triazole compound.
There is a continuing need for improved azole wood preservative and waterproofing compositions and azole antifungal compositions.
Applicants have discovered that amine oxides enhance the performance of azoles as fungicides and wood preservatives. Also, amine oxides have been found to provide waterproofing properties and enhance the uniform distribution and penetration of azoles into wood substrates. The present invention provides a composition comprising an amine oxide and an azole, such as a 1,2,4-triazole. The composition of the present invention may be incorporated into or be a wood preservative and waterproofing system, or agricultural product.
Another embodiment of the present invention is a method for preserving and/or waterproofing a wood substrate by applying the composition to the wood substrate.
Yet another embodiment is an article comprising a wood substrate and the composition of the present invention.
The invention also provides a method of controlling fungi comprising applying an effective amount of the composition of the present invention to the fungi or the area on which the fungi grow.
The present invention provides a composition comprising an amine oxide and an azole. Surprisingly, the fungicidal activity of the azole/amine oxide composition is substantially greater than the sum of the fungicidal activities of the amine oxides and azole separately.
The amine oxide also enhances the uniform distribution and penetration of the azole into wood substrates and improves leach resistance. Furthermore, the azole compositions of the present invention have high water solubility and low volatility.
The compositions of the present invention are useful as wood preservatives for protecting wood from staining, discoloring, molding, rotting and losing its mechanical properties. Wood products which can be preserved with the composition include, but are not limited to, timber, lumber, railway tiles, telephone poles, fences, windows and doors, plywood, particle board, oriented-strained board, chipboard, joinery, bridges and wood products which are generally used in houses, building, construction and carpentry.
The compositions are also useful in textile fibers, e.g., cotton and wool natural fibers and polyamide and polyester synthetic fibers; coatings, e.g., oil paints, dispersion paint, lacquers, and finishing stains; and adhesives and other materials which are degradable by fungi. The compositions may also advantageously be applied in the cellulose and paper industry, in particular to protect pulpwood for paper manufacture from fungal attack.
Additionally, the compositions are useful for industrial preservation to protect products from microbiological attack or degradation, which reduces or destroys their economic value. Examples of such products include, but are not limited to, latexes, adhesives, cellulose products, metal working fluids, coatings, and paint compositions.
The compositions of the present invention are effective against a broad range of fungi. Examples of such fungi include, but are not limited to, Ascomycetes (e.g., Venturia, Podosphaera, Erysiphe, Monilinia, Uncinula, Aureobasidium, Sclerophoma); Basidiomycetes (e.g., Hemileia, Rhizoctonia, Puccinia, Coniophora, Serpula, Poria, Uromyces, Gloeophyllum, Lentinus, Coriolus, Irpex); and fungi imperfecti (e.g., Botrytis, Helminthosporium, Rhynchosporium, Fusarium, Septoria, Cercospora, Alternaria, Pyricularia, Penicillium, Geotrichum).
The amine oxide may be a trialiphatic substituted amine oxide, an N-alkylated cyclic amine oxide, a dialkylpiperazine di-N-oxide, an alkyldi(poly(oxyalkylene))amine oxide, a dialkylbenzylamine oxide, a fatty amidopropyldimethyl amine oxide, a diamine oxide; a triamine oxide, or any combination of any of the foregoing. Preferably, the amine oxide includes at least one C8-C18 alkyl moiety.
Preferred trialiphatic substituted amine oxides have the formula R1R2R3Nxe2x86x92O, where R1 is a linear, branched, cyclic or any combination thereof C8 to C40 saturated or unsaturated group; and R2 and R3 independently are linear, branched, or any combination thereof C1 to C40 saturated or unsaturated groups. R1, R2, and R3 independently may be alkyl, alkenyl, or alkynyl groups. More preferably, R1 is a linear, branched, cyclic or any combination thereof C8 to C22 saturated or unsaturated group, such as coco, hydrogenated tallow, soya, decyl, hexadecyl, and oleyl; and R2 and R3 independently are linear, branched, or any combination thereof C1 to C22 saturated or unsaturated groups, such as coco, hydrogenated tallow, soya, decyl, and hexadecyl.
A preferred trialiphatic substituted amine oxide is a dialkylmethylamine oxide having the formula R1R2CH3Nxe2x86x92O, where R1 and R2 are defined as above. Another preferred trialiphatic substituted amine oxide is an alkyldimethylamine oxide having the formula R1(CH3)2Nxe2x86x92O, where R1 is defined as above. More preferred alkyldimethylamine oxides have the formula R19(CH3)2Nxe2x86x92O, where R19 is a linear or branched C8-C18 alkyl or alkenyl. Preferably, R19 is a linear or branched C8-C16 alkyl. Alkyldimethylamine oxides are non-toxic and non-mutagenic surfactants. Suitable alkyldimethylamine oxides include, but are not limited to, a C10 alkyldimethylamine oxide, a C10-C14 alkyldimethylamine oxide, a C12-C16 alkyldimethylamine oxide, a C16-C18 alkyldimethylamine oxide, and any combination of any of the foregoing.
Preferred N-alkylated cyclicamine oxides have the formula R4R5R6Nxe2x86x92O where R4 is defined as R1 above and R5 and R6 are linked to form a cyclic group. The cyclic group typically contains from 4 to 10 carbon atoms and may optionally contain oxygen, sulfur, nitrogen, or any combination of any of the foregoing. More preferred N-alkylated cyclicamine oxides include, but are not limited to, an alkylmorpholine N-oxide, a dialkylpiperazine di-N-oxide, and any combination of any of the foregoing.
Preferred alkylmorpholine N-oxides have the formula 
where R7 is defined as R1 above. According to a more preferred embodiment, R7 is a linear or branched C8 to C16 alkyl. Examples of preferred alkylmorpholine N-oxides include, but are not limited to, cetyl morpholine N-oxide and lauryl morpholine N-oxide.
Preferred dialkylpiperazine di-N-oxides have the formula 
where R8 is defined as R1 above and R9 is defined as R2 above.
Preferred alkyldi(poly(oxyalkylene))amine oxides have the formula 
where R10 is defined as R1 above; R11 and R12 independently are H or CH3; and m and n independently are integers from about 1 to about 10.
Preferred dialkylbenzylamine oxides have the formula R13R14R15Nxe2x86x92O, where R13 is defined as R1 above; R14 is defined as R2 above; and R15 is benzyl. More preferred dialkylbenzylamine oxides include, but are not limited to, alkylbenzylmethylamine oxides having the formula R13R15CH3Nxe2x86x92O where R13 and R15 are defined as above. According to a more preferred embodiment, R13 is a linear or branched C8-C12 alkyl.
Preferred fatty amidopropyldimethyl amine oxides have the formula 
where R16 is defined as R1 above.
Preferred diamine oxides have the formula 
where R17 is defined as R1 above; and m is an integer from about 1 to about 10.
Preferred triamine oxides have the formula 
where R18 is defined as R1 above; and m and n independently are integers from about 1 to about 10.
Long chain (C16 or greater) amine oxides, such as hexadecylamine oxides and hydrogenated tallow amine oxides, are particularly preferable for imparting waterproofing properties to the composition. Short chain (C14 and shorter) amine oxides aide in solubilizing the azole and long chain amine oxides.
The azole is preferably a 1,2,4-triazole. Suitable 1,2,4-triazoles include, but are not limited to, triadimefon, triadimenol, triazbutil, propiconazole, cyproconazole, difenoconazole, tebuconazole, myclobutanil, triadimenol, fenbuconazole, etaconazole, bromoconazole, flusiazole, uniconazole, diniconazole, bitertanol, hexaconazole, azaconazole, flutriafol, epoxiconazole, fluquinoconazole, tetraconazole, penconazole, and any combination of any of the foregoing. Preferred azoles include, but are not limited to triadimefon, propiconazole, cyproconazole, tebuconazole, myclobutanil, fenbuconazole, and any combination of any of the foregoing. More preferably, the azole is propiconazole, tebuconazole, or any combination of any of the foregoing. The azole may also be a benzimidazole, such as thiabendazole, benomyl, and carbendazim.
A preferred amine oxide/azole combination is a C10-C16 alkyl dimethylamine oxide or a mixture of C10-C16 alkyl dimethylamine oxides with propiconazole, cyproconazole, tebuconazole, or a combination thereof. More preferred C10-C16 alkyl dimethylamine oxides for these combinations include, but are not limited to, coco-dimethylamine oxide, a mixture of branched C10-C14 alkyl dimethyl amine oxides, and any combination of any of the foregoing.
The composition may include a solvent, such as water and water miscible solvents, including, but not limited to, alcohols, glycols, esters, ethers, polyethers, amides, and any combination of any of the foregoing.
The weight ratio of amine oxide to azole broadly ranges from about 5000:1 to about 0.1:1 and preferably ranges from about 100:1 to about 1:1. According to one preferred embodiment, the weight ratio ranges from about 40:1 to about 5:1 and is more preferably about 20:1.
According to one embodiment of the invention, the composition in concentrated form contains broadly from about 5 to about 100%, preferably from about 10 to about 50%, and more preferably from about 10 to about 35% by weight of combined amine oxide and azole based upon 100% weight of total composition.
Use dilutions of the composition typically comprise a fungicidally effective amount of azole and amine oxide. Generally, the use dilution comprises a fungicide enhancing effective amount of amine oxide, i.e., an amount of amine oxide sufficient to enhance the fungicidal efficacy of the azole. For wood applications, the use dilution may comprise a wood distribution, penetrating enhancing, waterproofing, and/or fungicide enhancing effective amount of amine oxide and a fungicidally effective amount of azole. Use dilutions preferably comprise from about 0.01 to about 5.0%, more preferably from about 0.1 to about 5.0%, and most preferably from about 0.5 to about 5.0% by weight of amine oxide, based upon 100% weight of total composition. Use dilutions preferably comprise from about 0.00001% (0.1 ppm) to about 2.0%, more preferably from about 0.0001% (1 ppm) to about 1.0%, and most preferably from about 0.0005% (5 ppm) to about 0.5% by weight of azole, based upon 100% weight of total composition.
The composition may be incorporated into or be a wood preservative and/or waterproofing system or an agricultural product.
Other adjuvants may be included in the composition as known to one of ordinary skill in the art. Examples of such adjuvants include, but are not limited to, thickeners, drying oils, anti-oxidants, UV absorbers, pigments, waxes, and any combination of any of the foregoing. Other biocides, fungicides and insecticides may be include in the composition. Any organic insecticide or fungicide that can be solubilized by an aqueous amine oxide solution is suitable for use in the present composition. Suitable insecticides include, but are not limited to, chloropyrifos, folpet, captafol, captan, pyrethroids, and any combination of any of the foregoing. Suitable fungicides include, but are not limited to, iodopropargyl butylcarbamate, tributyltin oxide, 2-(thiocyanomethylthio)benzothiazole, iodo-sulfones, azoles, isothiazalones, and any combination of any of the foregoing.
Another embodiment of the present invention is a method for preserving and/or waterproofing a wood substrate by applying the composition of the present invention to the wood substrate. The composition may be applied to the wood substrate by any method known to one of ordinary skill in the art. For example, the composition may be applied by treating the wood substrate under pressure or vacuum, in a thermal or dip system. Alternatively, it may be applied by a surface treatment, such as brushing, dipping, soaking, and spraying.
The invention also includes a method of controlling fungi comprising applying an effective amount of one or more compositions of the present invention. The term xe2x80x9ccontrollingxe2x80x9d as used herein includes, but is not limited to, inhibiting growth of fungi.
The composition of the present invention may be prepared by mixing the azole, amine oxide, solvents, and adjuvants. The mixture may be heated and/or stirred to expedite mixing.